KR20180042839A - Curable resin composition, composition for molding, resin molding, and method for manufacturing resin molding - Google Patents

Abstract

Disclosed is a curable resin composition containing a radically polymerizable monomer containing a monofunctional radically polymerizable monomer, a linear or branched polymer containing a polyoxyalkylene chain, and a radical polymerization initiator.

Description

Curable resin composition, composition for molding, resin molding, and method for manufacturing resin molding

TECHNICAL FIELD The present invention relates to a curable resin composition, a molding composition, a resin molded article, and a method for producing a resin molded article.

There is a demand for a material having excellent mechanical properties such as hardness that is hard to be deformed and strength and flexibility that are not broken even if deformed. One method of improving the strength of a resin molded article is a method of forming a three-dimensional crosslinked structure. According to this method, the hardness is improved, but the molded article tends to be fragile and fragile.

As a method for improving strength and flexibility, for example, a method of dispersing an elastomer component, which is likely to be deformed, such as acrylic rubber, in a resin to relax stress is generally known. It is also known that the strength of a resin molded article may be improved by adding a high molecular weight component to the resin. As the strength improving mechanism, entanglement of the polymer chains is promoted.

In recent years, attention has been paid to the crosslinked structure of a polymer, and an approach for improving the strength by alleviating stress concentration on the crosslinked site at the time of deformation has been proposed. For example, a molecular design that relaxes stress concentration between crosslinked points by forming crosslinked sites reversibly, forms crosslinked structures that can move freely by forming a pseudo-crosslinked structure called pulley effect, and thereby relieves stress concentration It is proposed.

On the other hand, metals, resins, ceramics, and the like are known as shape memory materials. Generally, shape memory is expressed based on a phase transformation due to a change in crystal structure or a change in molecular motion pattern. In many cases, the shape memory material has characteristics that it is excellent in vibration damping properties and the like in addition to shape recovery properties. Up to now, metal and resin have been mainly studied as shape memory materials.

The shape memory resin is a resin that is restored to its original shape when heated to a temperature higher than a certain temperature even if a force is applied and deformed after molding. Compared with shape memory alloys, shape memory resins are generally superior in terms of low cost, high shape change rate, light weight, easy processing, and coloring.

The shape memory resin is soft at high temperature and easily deformed like rubber. On the other hand, it is hard at low temperature and hard to deform like glass. The shape memory resin can be stretched up to several times its original length by a small force at high temperature and can keep its deformed shape by cooling. In this state, when the material is heated under no load, the material is restored to its original shape. At high temperatures, the material just returns to its original shape by removing the force. Therefore, the characteristics of absorption and storage of energy at a high temperature can be utilized.

As the main shape-memory resin, there are polynorbornene, transisoprene, styrene-butadiene copolymer and polyurethane. For example, Patent Document 5 describes a norbornene resin, Patent Document 6 describes a trans-isoprene-based resin, Patent Document 7 describes a polyurethane-based resin, and Patent Document 8 describes a shape memory resin relating to an acrylic resin.

Patent Document 1: JP-A-60-36558 Patent Document 2: JP-A-2016-8232 Patent Document 3: JP-A-2004-35853 Patent Document 4: Japanese Patent No. 3475252 Patent Document 5: Japanese Patent Publication No. Hei 5-72405 Patent Document 6: Japanese Patent Application Laid-Open No. 2004-250182 Patent Document 7: JP-A-2004-300368 Patent Document 8: JP-A-7-292040

It is an object of one aspect of the present invention to provide a curable resin composition capable of forming a resin molded article having a high elongation at break and excellent in shape recovery after being deformed under stress.

Another object of the present invention is to provide a resin molded article having shape memory property excellent in shape recovery property by heating.

One aspect of the present invention relates to a curable resin composition containing a radically polymerizable monomer containing a monofunctional radically polymerizable monomer, a linear or branched polymer containing a polyoxyalkylene chain, and a radical polymerization initiator.

This curable resin composition can form a resin molded product having excellent fracture toughness and excellent shape recovery after being deformed under stress.

Another aspect of the present invention is a compound of formula (I):

, Wherein X, R ¹ and R ² are each independently a divalent organic group and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, and a monofunctional radically polymerizable monomer, To a resin molded article containing a first polymer contained as a unit and a linear or branched second polymer.

The resin molded article may have a storage elastic modulus at 25 占 폚 of 0.5 MPa or more. Alternatively, the resin molded article may have shape memory property. Such a resin molded article is excellent in shape recovery property by heating.

Another aspect of the present invention relates to a molding composition comprising a radically polymerizable monomer (reactive monomer) comprising a radically polymerizable compound of formula (I) and a monofunctional radically polymerizable monomer, and a second polymer. When the radical polymerizable monomer is polymerized in the presence of the second polymer, the molding composition can form a resin molded article having a storage elastic modulus of at least 0.5 MPa at 25 캜. Alternatively, the molding composition can form a resin molded article having shape memory property when the radical polymerizable monomer is polymerized in the presence of the second polymerizable monomer.

Another aspect of the present invention relates to a method of producing a resin molded article comprising a first polymer and a second polymer. This method is characterized in that, in a molding composition comprising a radically polymerizable monomer containing a radically polymerizable compound of formula (I) and a monofunctional radically polymerizable monomer, and a second polymer, And a step of producing a polymer.

According to one aspect of the present invention, there is provided a curable resin composition capable of forming a resin molded article excellent in shape recovery after being deformed under stress with high breaking elongation. The curable resin composition according to some forms can form a resin molded article having high strength, good toughness and transparency. Here, the fact that the resin molded article is excellent in shape recoverability after being deformed by stress means that the resin molded article is easily recovered to the shape before being subjected to stress only by being released from the stress. It does not necessarily mean having sex.

Formation of a conventional crosslinked structure using a dynamic bond formation or a pulley effect requires a complicated molecular design, which is also problematic in terms of cost and mass productivity. The formation of the pseudo-crosslinked structure using the entanglement of the main chain by the addition of the high molecular weight component is easy, but the sufficient effect can not be obtained at present. In addition, since a relatively large amount of a high molecular weight component is required, there are many cases in which thickening and lowering of compatibility are a problem. According to the present invention, it is possible to provide a curable resin composition which can easily form a molded article having good mechanical properties as compared with these conventional methods.

According to another aspect of the present invention, there is provided a resin molded article having shape memory property excellent in shape recovery property by heating. The elastic modulus of the resin molded article of the present invention can be controlled to easily increase the shape recovery speed upon heating. The resin moldings according to several forms are excellent in various properties such as transparency, flexibility, stress relaxation property and water resistance.

1 is a perspective view showing an embodiment of a resin molded article.

Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

(Curable resin composition)

The curable resin composition according to one embodiment contains a radical polymerizable monomer containing a monofunctional radically polymerizable monomer and a linear or branched polymer containing a polyoxyalkylene chain (hereinafter sometimes referred to as " modifying polymer " ), And a radical polymerization initiator. The modifying polymer generally does not have a radically polymerizable group and is contained in the curable resin composition as a component separate from the radical polymerizable monomer.

The plurality of oxyalkylene groups constituting the polyoxyalkylene chain in the modifying polymer may be mutually the same or different. The polyoxyalkylene chain may be a random copolymer in which two or more oxyalkylene groups are irregularly arranged, or may be a block copolymer containing a block in which the same oxyalkylene group is continuously bonded. The polyoxyalkylene chain can be derived, for example, from polyethers such as polyalkylene glycols.

The polyoxyalkylene chain in the modifying polymer may be a polyoxyethylene chain, a polyoxypropylene chain, a polyoxybutylene chain, or a combination thereof. In particular, the polyoxyalkylene chain in the modifying polymer may be a polyoxyethylene chain, a polyoxypropylene chain, or a combination thereof.

The proportion of the polyoxyalkylene chain in the modifying polymer may be from 20 to 60 mass% based on the mass of the modifying polymer. Thus, the effect of improving the mechanical properties of the resin molded article according to the present invention is further remarkably exerted.

The polyoxyethylene chain is easily entangled with a molecular chain of a polymer formed by polymerization of a radically polymerizable monomer including a mono-functional radically polymerizable monomer, and also has a structure in which a moiety where entanglement occurs can freely move . That is, it is considered that a pseudo-crosslinked structure in which a polyoxyethylene chain is entangled with a molecular chain of another polymer allows a tangled point to freely slide and move is formed. When the pseudo-crosslinked structure is formed, the stress applied to each crosslinking point is uniformly dispersed when the resin molded article is deformed, thereby improving the strength and elongation of the resin molded article.

The proportion of the polyoxyethylene chain may be 20 mass% or more, 30 mass% or more, or 40 mass% or more based on the mass of the whole polyoxyalkylene chain in the modifying polymer. When the ratio of the polyoxyethylene chain is large to some extent, the resin molded article after curing may have particularly excellent mechanical properties in terms of strength and elongation. The proportion of the polyoxyethylene chain may be 70 mass% or less, 60 mass% or 50 mass% or less, based on the total mass of the polyoxyalkylene chain in the modifying polymer. As a result, the crystallinity of the modifying polymer is suppressed. By inhibiting the crystallization, the modifying polymer tends to have high compatibility with other components and can have a suitably low viscosity.

The number average molecular weight of the polyoxyalkylene chain constituting the modifying polymer is not particularly limited, but may be, for example, 500 or more, 1000 or more, or 3000 or more. When the molecular weight of the polyoxyalkylene chain is large, the formation of the pseudo-crosslinked structure tends to be promoted. The number average molecular weight of the polyoxyalkylene chain may be 20,000 or less, 15,000 or less, or 10000 or less. Accordingly, the modifying polymer tends to have high compatibility with other components and can have a suitably low viscosity. In the present specification, the number average molecular weight and the weight average molecular weight refer to a standard polystyrene conversion value obtained by gel permeation chromatography, unless otherwise defined.

The modifying polymer may contain two or more polyoxyalkylene chains and a linking group linking them. The modifying polymer having a linking group includes, for example, a molecular chain represented by the following formula (X). In the formula (X), R ²¹ represents an oxyalkylene group, n ¹¹ , n ¹² and n ¹³ each independently represents an integer of 1 or more, and L represents a linking group. A plurality of R ²¹ and L in the same molecule may be the same or different.

The oxyalkylene group of R < ²¹ > is, for example, represented by the following formula (Y). In the formula (Y), R ²² represents a hydrogen atom or an alkyl group having 4 or less carbon atoms, and n ²⁰ represents an integer of 2 to 4. A plurality of R < ²² > and n < ²⁰ > in the same molecule may be the same or different.

The linking group (L) in the formula (X) is a divalent organic group connecting two polyoxyalkylene chains. The linking group (L) may be an organic group containing a cyclic group or an organic group branched. The connector L may be, for example, a divalent group represented by the following formula (30).

R ³⁰ includes a cyclic group, a cyclic group having two or more cyclic groups, a group bonded directly or via an alkylene group, or a carbon atom containing a hetero atom selected from an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom Or an organic group having a branched structure which may be present. Z ⁵ and Z ⁶ are divalent groups which combine with R ³⁰ and linear polyoxyalkylene chains and are, for example, -NHC (═O) -, -NHC (═O) O-, -O-, -OC O) -, -S-, -SC (= O) -, -OC (= S) - or -NR ¹⁰ - (R ¹⁰ is a hydrogen atom or an alkyl group).

The cyclic group contained in the linking group (L) may contain a hetero atom selected from a nitrogen atom and a sulfur atom. The cyclic group contained in the linking group (L) may be, for example, a cyclic group, a cyclic ether group, a cyclic amine group, a cyclic thioether group, a cyclic ester group, a cyclic amide group, a cyclic thioester group, an aromatic hydrocarbon group, Or a combination thereof. Specific examples of cyclic groups included in linking group (L) include 1,4-cyclohexanediyl group, 1,2-cyclohexanediyl group, 1,3-cyclohexanediyl group, 1,4-benzenediyl group, A 3-benzenediyl group, a 3-benzenediyl group, a 1,2-benzenediyl group and a 3,4-furanediyl group.

Examples of the branching organic group (R ³⁰ in the formula (30)) included in the linking group (L) include a lysine triyl group, a methyl silanetriyl group and a 1,3,5-cyclohexanetriyl group.

The coupler L represented by the formula (30) may be a coupler represented by the following formula (31). R ³¹ in the formula (31) represents a single bond or an alkylene group. R ³¹ may be an alkylene group having 1 to 3 carbon atoms. Z ⁵ and Z ⁶ are the same as in the formula (30).

By introducing a cyclic structure or a branched structure having a large volume in the connecting unit L, it is difficult to eliminate the entanglement of the molecular chains formed by the polyoxyalkylene chains when the resin molded body is deformed under stress do. This inventor believes that this contributes to both the high elongation of the resin molded article and the appearance of shape recoverability after being deformed.

The weight-average molecular weight of the modifying polymer is not particularly limited, but may be, for example, 3000 or more, 5000 or more, or 8000 or more, and 150000 or less, 100000 or less, or 50000 or less. When the weight average molecular weight of the modifying polymer is within these numerical ranges, the modifying polymer tends to have good compatibility with other components, and the resin molded article may have particularly excellent mechanical properties in terms of strength and elongation.

The modifying polymer can be obtained by a usual synthesis method using a conventionally available raw material as a starting material, as understood by those skilled in the art. For example, the modifying polymer may include a polyoxyalkylene chain and a bifunctional alcohol having a hydroxyl group bonded to both terminals thereof (such as a polyalkylene glycol), a functional group reactive with a hydroxyl group (isocyanate group, etc.), and a cyclic group or a branched group (Such as a bimetallic isocyanate). The modifying polymer to be synthesized may contain a branched structure based on a side reaction such as trimerization of an isocyanate group. When a bifunctional alcohol is used as a starting material for synthesis, its number average molecular weight may be 500 to 20,000.

The structure of the modifier polymer can be specified, for example, by the molecular weight and the molecular weight distribution, the linkage, and the structure and proportion of the oxyalkylene chain. However, the structure of the modifying polymer can be largely changed by other points, for example, the arrangement of the constituent units and the steric structure. However, it is generally difficult to identify the arrangement of constituent units in a realistic way. Therefore, in order to specify the structure of the modifying polymer, it may be necessary to specify the conditions for synthesis or the kind and ratio of raw materials to be used.

The content of the modifying polymer in the curable resin composition may be 1% by mass or more, 3% by mass or more, or 5% by mass or more based on the mass of the curable resin composition. As a result, the effect of improving the mechanical properties of the resin molded article by the modifying polymer is particularly remarkable. The content of the modifying polymer may be 20 mass% or less, 15 mass% or less, or 10 mass% or more. Thus, high compatibility with other components of the modifying polymer can be ensured. If the compatibility is high, it is easy to obtain a transparent resin molded article free from phase separation.

The radically polymerizable monomer contained in the curable resin composition includes a monofunctional radically polymerizable monomer having one radically polymerizable group. The radical polymerizable monomer may include, for example, alkyl (meth) acrylate and / or acrylonitrile as the monofunctional radically polymerizable monomer.

The alkyl (meth) acrylate is an alkyl (meth) acrylate having an alkyl group of 1 to 16 carbon atoms which may have a substituent (an ester of (meth) acrylic acid with an alkyl alcohol of 1 to 16 carbon atoms which may have a substituent) good. The substituent that the alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms may have may contain an oxygen atom and / or a nitrogen atom.

Since the radical polymerizable monomer contains an alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms, the resistance to scratching of the resin molded article tends to be improved. The use of an alkyl (meth) acrylate having an alkyl group having a small number of carbon atoms tends to improve the durability of the resin molded article after curing. From this viewpoint, the radically polymerizable monomer may include an alkyl (meth) acrylate having an alkyl group having 1 to 10 carbon atoms or 1 to 8 carbon atoms, which may have a substituent, as the monofunctional radically polymerizable monomer.

The proportion of the alkyl (meth) acrylate having 1 to 16 carbon atoms which may have a substituent in the curable resin composition is preferably 10 mol% or more, 15 mol% or more, or 20 mol% or more based on the total amount of the radical polymerizable monomer Mol% or more, 95 mol% or less, 90 mol% or less, or 85 mol% or less. When the proportion of the alkyl (meth) acrylate having 1 to 16 carbon atoms which may have a substituent is within these ranges, it is easy to obtain a resin molded article excellent in adhesion and resistance to aging. The proportion of the alkyl (meth) acrylate having 1 to 10 carbon atoms which may have a substituent may be 8 mol% or more, 10 mol% or more, or 15 mol% or more based on the total amount of the radical polymerizable monomer, 55 mol% or less, 45 mol% or less, or 25 mol% or less. When the ratio of the alkyl (meth) acrylate having an alkyl group having 10 or less carbon atoms which may have a substituent is within the above range, a resin molded article having good adhesion and resistance is more likely to be formed.

Examples of the alkyl (meth) acrylate having 1 to 16 carbon atoms which may have a substituent include ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, Ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl acrylate, 1-methylethyl methacrylate, 2-methoxyethyl acrylate (MEA), N, N-dimethylaminoethyl acrylate and glycidyl methacrylate. These may be used alone or in combination of two or more. For example, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate can be used as alkyl (meth) acrylates having 1 to 16 carbon atoms which may have a substituent.

The radically polymerizable monomer may contain acrylonitrile as the monofunctional radically polymerizable monomer. As a result, the bending resistance of the resin molded article tends to be improved. The combination of acrylonitrile and (meth) acrylate having an alkyl group having 1 to 16 carbon atoms (or 1 to 10 carbon atoms) is particularly advantageous for obtaining a resin molded article having improved bending resistance.

The proportion of acrylonitrile in the curable resin composition may be not less than 40 mol%, not less than 50 mol%, or not less than 70 mol%, not more than 90 mol% and not more than 85 mol%, based on the total amount of the radical polymerizable monomer Or 80 mol% or less. When the ratio of acrylonitrile is within these ranges, a more favorable effect can be obtained with respect to the bending resistance and the high degree of high strength.

The radical polymerizable monomer may include one or more compounds selected from vinyl ether, styrene and styrene derivatives as monofunctional radically polymerizable monomers. Examples of vinyl ethers include vinyl butyl ether, vinyl octyl ether, vinyl-2-chloroethyl ether, vinyl isobutyl ether, vinyl dodecyl ether, vinyl octadecyl ether, vinyl phenyl ether and vinyl cresyl ether. Examples of the styrene derivative include alkyl styrene, alkoxystyrene (? -Methoxystyrene, p-methoxystyrene, etc.) and m-chlorostyrene.

The radical polymerizable monomer may include other monofunctional radically polymerizable monomers and / or multifunctional radically polymerizable monomers. Examples of other monofunctional radically polymerizable monomers include vinylphenol, N-vinylcarbazole, 2-vinyl-5-ethylpyridine, isopropenyl acetate, vinylisocyanate, vinylisobutylsulfide, Vinylbenzyl ethylcarbinol, vinylphenylsulfide, allyl acrylate,? -Chloroethyl acrylate, allyl acetate, 2,2,6,6-tetramethyl-piperidinyl methane N-vinylpyrrolidone, N-vinylpyrrolidone, N, N-diethyl vinylcarbamate, vinyl isopropenyl ketone, N-vinylcaprolactone, vinylformate, p- vinylbenzylmethylcarbinol, vinylethylsulfide, vinylferrocene, vinyldichloroacetate, N-vinylpyrrolidone, vinylmethylsulfide, N-vinyloxazolidone, vinylmethylsulfoxide, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylsuccinimide, allyl alcohol, norbornadiene, diallyl melamine, -N'-ethyl-urea and acenaphthalene.

The various radical polymerizable monomers exemplified above may be used alone or in combination of two or more.

The curable resin composition may contain a radical polymerization initiator for polymerization of a radically polymerizable monomer. The radical polymerization initiator may be a thermal radical polymerization initiator, a photo radical polymerization initiator, or a combination thereof. The content of the radical polymerization initiator is appropriately adjusted within a usual range, but may be, for example, from 0.01 to 5% by mass based on the mass of the curable resin composition.

Examples of the thermal radical polymerization initiator include organic peroxides such as ketone peroxide, peroxyketal, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxydicarbonate, and hydroperoxide, sodium persulfate, potassium persulfate, Azobisisobutyronitrile (AIBN), 2,2'-azobis-2,4-dimethylvaleronitrile (ADVN), 2,2'-azobis- Azo compounds such as 2-methylbutyronitrile and 4,4'-azobis-4-cyanovaleric acid, alkyl metals such as sodium ethoxide and tert-butyllithium, 1-methoxy- 2-methyl-1-propene), and the like.

A thermal radical polymerization initiator and a catalyst may be combined. Examples of the catalyst include a metal salt and a compound having a reducing property such as a tertiary amine compound such as N, N, N ', N'-tetramethylethylenediamine.

As the photo radical polymerization initiator, 2,2-dimethoxy-1,2-diphenylethane-1-one can be mentioned. As a commercially available product, there is Irgacure 651 (manufactured by Nippon Chiba Chemical Co., Ltd.).

The curable resin composition may contain a solvent as required, or may be substantially solventless. Examples of the solvent to be used include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; aliphatic solvents such as hexane and methylcyclohexane; And hydrocarbon-based solvents. These may be used alone or in combination of two or more.

The content of the solvent contained in the curable resin composition can be appropriately selected depending on the purpose and the like. For example, the curable resin composition can be used as a solution or dispersion in which the concentration of the solid component (component other than the solvent) is about 20 mass% to 99 mass% of the total.

The curable resin composition may contain at least one component selected from the group consisting of a binder polymer, a light-coloring agent, a heat-coloring agent, a plasticizer, a pigment, a filler, a flame retardant, a stabilizer, an adhesion imparting agent, a leveling agent, . These may be used alone or in combination of two or more. When the curable resin composition contains other components, the content thereof may be 0.01 mass% or more, and 30 mass% or less, based on the total mass of the curable resin composition.

The curable resin composition may be a liquid, semi-solid or solid. The curable resin composition before curing may be a film type.

The curable resin composition can be used as a molding composition or coating for forming a resin molded article, a surface coating material, an adhesive, or the like. The formed resin molded article may have any shape including film, sheet, plate, fiber, rod, cylinder, cylinder, plate, disk, spiral, 1 is a perspective view showing an embodiment of a resin molded article. The resin molding 1 shown in Fig. 1 is an example of a flat plate-like molding. The resin molded product after curing may be further processed by various methods such as machining.

The resin molded article can be produced by a method comprising a step of producing a polymer in a curable resin composition by radical polymerization of a radically polymerizable monomer. Radical polymerization of a radically polymerizable monomer can be initiated by heating or irradiation of an actinic ray such as ultraviolet rays. The film-shaped resin molded article can be formed, for example, by applying a curable resin composition on the surface of a base material, drying the applied curable resin composition if necessary, and then radically polymerizing the radical polymerizable monomer by heat or light .

The temperature of the polymerization reaction is not particularly limited, but when the resin composition contains a solvent, the temperature is preferably not higher than its boiling point. The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas, helium gas or argon gas. As a result, inhibition of polymerization by oxygen is suppressed, and a resin molding of good quality can be stably obtained.

(Composition for molding)

The molding composition according to one embodiment comprises a compound represented by formula (I):

, A radically polymerizable monomer comprising a monofunctional radically polymerizable monomer, and a second polymer. In formula (I), X, R ¹ and R ² are each independently a divalent organic group, and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group. The radical polymerizable monomer is polymerized in the molding composition to produce a first polymer composed of monomer units derived from these radical polymerizable monomers. As a result, the reaction product is cured to form a resin molded product (cured product). The first polymer is usually not bonded to the second polymer by a covalent bond, but is formed in the molded body as a polymer separate from the second polymer.

The first polymer may include a cyclic monomer unit represented by the following formula (II) derived from the compound of formula (I). It is believed that the cyclic monomer unit of the formula (II) contributes to the expression of specific properties such as shape memory of the resin molded article. However, the first polymer may not necessarily contain the monomer unit of formula (II).

X in the formulas (I) and (II) represents, for example, the following formula (10):

May also be displayed. In formula (10), Y is a cyclic group which may have a substituent, Z ¹ and Z ² are each independently a functional group containing an atom selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom, i and j Are each independently an integer of 0 to 2. * Denotes the combined number (hand) (this is true in other equations). When X is a group of the formula (10), the cyclic monomer unit of the formula (II) is considered to be particularly easy to form. The arrangement of Z ¹ and Z ² with respect to the annular ring Y may be a cis position or a trans position. Z ¹ and Z ² is -O-, -OC (= O) - , -S-, -SC (= O) -, -OC (= S) -, -NR 10 - (R 10 is a hydrogen atom or an alkyl group; ), Or a group represented by -ONH-.

Y may be a cyclic group having from 2 to 10 carbon atoms, and may contain a hetero atom selected from an oxygen atom, a nitrogen atom and a sulfur atom. The cyclic group Y may be, for example, a cyclic group, a cyclic ether group, a cyclic amine group, a cyclic thioether group, a cyclic ester group, a cyclic amide group, a cyclic thioester group, an aromatic hydrocarbon group, a heteroaromatic hydrocarbon group, have. The cyclic ether group may be a cyclic group having a monosaccharide or a polysaccharide. Specific examples of Y include, but are not particularly limited to, cyclic groups represented by the following formulas (11), (12), (13), (14) or (15) From the viewpoint of the stress relaxation property of the resin molded article, Y may be a group of the formula (11) (particularly 1,2-cyclohexanediyl group).

R ¹ and R ² in the formulas (I) and (II) may be mutually the same or different and may be a group represented by the following formula (20).

In the formula (20), R ⁶ is a hydrocarbon group (alkylene group or the like) having 1 to 8 carbon atoms and is bonded to the nitrogen atom in formula (I) or formula (II). Z ³ is a group represented by -O- or -NR ¹⁰ - (R ¹⁰ is a hydrogen atom or an alkyl group). When R ¹ and R ² are the groups of formula (20), it is considered that the cyclic monomer units of formula (II) are particularly susceptible to formation. The carbon number of R ⁶ may be 2 or more, and may be 6 or less or 4 or less.

One embodiment of the radically polymerizable compound of formula (I) is a compound represented by the following formula (Ia). ^{Y, Z 1, Z 2,} i and j where a, is defined in the same manner as equation (10).

Examples of the compound represented by formula (Ia) include compounds represented by the following formulas (I-1), (I-2), (I-3), ), The compound represented by the formula (I-7) or the compound represented by the formula (I-8).

The compounds exemplified above can be used alone or in combination of two or more.

The proportion of the radical polymerizable compound of formula (I) in the molding composition may be 0.01 mol% or more, 0.1 mol% or more, or 0.5 mol% or more based on the total amount of the radical polymerizable monomer, and 10 mol % Or less, 5 mol% or less, or 1 mol% or less. When the ratio of the radical polymerizable compound of the formula (I) is within these ranges, a more advantageous effect can be obtained in that a cured product having excellent mechanical properties such as elongation, strength and bending resistance can be obtained.

The compound of formula (I) can be synthesized by a usual synthesis method using a conventionally available starting material as understood by those skilled in the art. For example, the compound of formula (I) can be synthesized by reacting a cyclic diol compound or cyclic diamine compound with a compound having a (meth) acryloyl group and an isocyanate group.

The radical polymerizable monomer in the molding composition may include alkyl (meth) acrylate and / or acrylonitrile as the monofunctional radically polymerizable monomer.

The alkyl (meth) acrylate is an alkyl (meth) acrylate having an alkyl group of 1 to 16 carbon atoms which may have a substituent (an ester of (meth) acrylic acid with an alkyl alcohol of 1 to 16 carbon atoms which may have a substituent) good. The substituent that the alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms may have may contain an oxygen atom and / or a nitrogen atom.

(Meth) acrylate having an alkyl group having 1 to 16 carbon atoms, it is possible to control the mechanical properties such as the modulus of elasticity, glass transition temperature (Tg) and elongation and strength of the cured product Effect can be obtained.

The proportion of the alkyl (meth) acrylate having 1 to 16 carbon atoms which may have a substituent in the molding composition is preferably 10 mol% or more, 15 mol% or more, or 20 mol% or more based on the total amount of the radical polymerizable monomer Or more, more preferably 95 mol% or less, 90 mol% or less, or 85 mol% or less. When the ratio of the alkyl (meth) acrylate having 1 to 16 carbon atoms which may have a substituent is within these ranges, a more favorable effect is obtained in that a cured product having excellent mechanical properties such as elongation and strength and excellent bending resistance can be obtained .

The use of an alkyl (meth) acrylate having an alkyl group having a small number of carbon atoms tends to increase the modulus of elasticity of the resin molded article after curing and to tend to exhibit shape memory property. From this viewpoint, the radically polymerizable monomer may include an alkyl (meth) acrylate having an alkyl group having not more than 10 carbon atoms, which may have a substituent, as the monofunctional radically polymerizable monomer. The proportion of the alkyl (meth) acrylate having 10 or less carbon atoms which may have a substituent in the molding composition is preferably 8 mol% or more, 10 mol% or more, or 15 mol% or less based on the total amount of the radical polymerizable monomer. Or less, 55 mol% or less, 45 mol% or less, or 25 mol% or less. When the ratio of the alkyl (meth) acrylate having an alkyl group having 10 or less carbon atoms which may have a substituent is within these ranges, a more advantageous effect is obtained in that a resin molded article having shape- Can be obtained. From the same viewpoint, the radical polymerizable monomer may contain (meth) acrylate having an alkyl group having not more than 8 carbon atoms, which may have a substituent, and the ratio may be in the above-mentioned numerical range.

Examples of the alkyl (meth) acrylate having 1 to 16 carbon atoms which may have a substituent include ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, Ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl acrylate, 1-methylethyl methacrylate, 2-methoxyethyl acrylate (MEA), N, N-dimethylaminoethyl acrylate and glycidyl methacrylate. These may be used alone or in combination of two or more.

Since the radical polymerizable monomer contains acrylonitrile, there is a tendency that a resin molded article having shape memory property tends to be formed, having excellent mechanical properties such as elongation and strength, and excellent bending resistance and a somewhat high modulus of elasticity. The combination of acrylonitrile and (meth) acrylate having an alkyl group having 1 to 16 carbon atoms (or 1 to 10 carbon atoms) is particularly advantageous for obtaining a resin molded article having a high modulus of elasticity. The proportion of acrylonitrile in the molding composition may be not less than 40 mol%, not less than 50 mol% or not less than 70 mol%, not more than 90 mol%, not more than 85 mol%, based on the total amount of the radical polymerizable monomer Or 80 mol% or less. When the ratio of acrylonitrile is within these ranges, a more advantageous effect can be obtained because the shape recovery is quick.

The radical polymerizable monomer may include one or more compounds selected from vinyl ether, styrene and styrene derivatives as monofunctional radically polymerizable monomers. Examples of vinyl ethers include vinyl butyl ether, vinyl octyl ether, vinyl-2-chloroethyl ether, vinyl isobutyl ether, vinyl dodecyl ether, vinyl octadecyl ether, vinyl phenyl ether and vinyl cresyl ether. Examples of the styrene derivative include alkyl styrene, alkoxystyrene (? -Methoxystyrene, p-methoxystyrene, etc.) and m-chlorostyrene.

The radical polymerizable monomer may include other monofunctional radically polymerizable monomers and / or multifunctional radically polymerizable monomers. Examples of other monofunctional radically polymerizable monomers include vinylphenol, N-vinylcarbazole, 2-vinyl-5-ethylpyridine, isopropenyl acetate, vinylisocyanate, vinylisobutylsulfide, Vinylbenzyl ethylcarbinol, vinylphenylsulfide, allyl acrylate,? -Chloroethyl acrylate, allyl acetate, 2,2,6,6-tetramethyl-piperidinyl methane N-vinylpyrrolidone, N-vinylpyrrolidone, N, N-diethyl vinylcarbamate, vinyl isopropenyl ketone, N-vinylcaprolactone, vinylformate, p- vinylbenzylmethylcarbinol, vinylethylsulfide, vinylferrocene, vinyldichloroacetate, N-vinylpyrrolidone, vinylmethylsulfide, N-vinyloxazolidone, vinylmethylsulfoxide, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylsuccinimide, allyl alcohol, norbornadiene, diallyl melamine, -N'-ethyl-urea and acenaphthalene.

The various radical polymerizable monomers exemplified above may be used alone or in combination of two or more.

The composition for molding contains the above-described radical polymerizable monomer and a linear or branched second polymer. The second polymer may be a polymer comprising two or more linear chains and a linking group linking the terminals thereof. This polymer includes, for example, a molecular chain represented by the following formula (B). In the formula (B), R ²⁰ is a monomer unit constituting a linear chain, n ¹ , n ² and n ³ are each independently an integer of 1 or more, and L is a linking group. A plurality of R < ²⁰ > and L in the same molecule may be the same or different.

The linear chain composed of the monomer unit R ²⁰ may be a molecular chain derived from a polyether, a polyester, a polyolefin, a polyorganosiloxane, or a combination thereof. Each linear chain may be a polymer or an oligomer.

Examples of linear chains derived from polyether include polyoxyalkylene chains such as polyoxyethylene chain, polyoxypropylene chain, polyoxybutylene chain, and combinations thereof. Polyoxyethylene chains are derived from polyethers such as polyalkylene glycols. Examples of linear chains derived from polyolefins include polyethylene chains, polypropylene chains, polyisobutylene chains, and combinations thereof. Examples of the linear chain derived from polyester include poly? Caprolactone chain. The linear chain derived from the polyorganosiloxane includes a polydimethylsiloxane chain. The second polymer may include a combination of two or more thereof, either alone or in combination.

The number average molecular weight of each linear molecular chain constituting the second polymer is not particularly limited, but may be, for example, 1000 or more, 3000 or more, or 5000 or more, and may be 80000 or less, 50000 or 20000 or less. In the present specification, the number average molecular weight means a standard polystyrene conversion value obtained by gel permeation chromatography unless otherwise defined.

The connector L is an organic or a branched organic group including a cyclic group. The connector L may be, for example, a divalent group represented by the following formula (30).

R ³⁰ includes a cyclic group, a cyclic group having two or more cyclic groups, a group bonded directly or via an alkylene group, or a carbon atom containing a hetero atom selected from an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom Or an organic group having a branched structure which may be present. Z ⁵ and Z ⁶ are divalent groups which combine with R ³⁰ and a linear chain and are, for example, -NHC (═O) -, -NHC (═O) O-, -O-, -OC -S-, -SC (= O) -, -OC (= S) - or -NR ¹⁰ - (R ¹⁰ is a hydrogen atom or an alkyl group). In the present specification, atoms at the end of the linear chain (atoms derived from monomers constituting the linear chain) are not generally interpreted as atoms constituting Z ⁵ or Z ⁶ . When it is not clear whether or not the atom at the end of the linear chain is an atom derived from the monomer, it may be interpreted that the atom is included in either the linear chain or the linking group.

The cyclic group contained in the linking group (L) may contain a hetero atom selected from a nitrogen atom and a sulfur atom. The cyclic group contained in the linking group (L) may be, for example, a cyclic group, a cyclic ether group, a cyclic amine group, a cyclic thioether group, a cyclic ester group, a cyclic amide group, a cyclic thioester group, an aromatic hydrocarbon group, Or a combination thereof. Specific examples of cyclic groups included in linking group (L) include 1,4-cyclohexanediyl group, 1,2-cyclohexanediyl group, 1,3-cyclohexanediyl group, 1,4-benzenediyl group, A 3-benzenediyl group, a 3-benzenediyl group, a 1,2-benzenediyl group and a 3,4-furanediyl group.

Examples of branched organic groups (for example, R ³⁰ in the formula (30)) included in the linking group (L) include lysine tri- group, methylsilanetriyl group and 1,3,5-cyclohexanetriyl group.

The coupler L represented by the formula (30) may be a coupler represented by the following formula (31). R ³¹ in the formula (31) represents a single bond or an alkylene group. R ³¹ may be an alkylene group having 1 to 3 carbon atoms. Z ⁵ and Z ⁶ are the same as in the formula (30).

The weight average molecular weight of the second polymer is not particularly limited, but may be, for example, 5000 or more, 7000 or more, or 9000 or more, 100000 or less, 80000 or less, or 60000 or less. Since the weight average molecular weight of the second polymer is within these numerical ranges, there is a tendency that good compatibility with other components of the second polymer and good various properties of the resin molded article tend to be obtained.

The second polymer can be obtained by a conventional synthetic method using a conventionally available raw material as a starting material, as will be understood by those skilled in the art. For example, a mixture containing a polyalkylene glycol having reactive terminal groups (such as a hydroxyl group), a polyester, a polyolefin, a polyorganosiloxane, or a combination thereof, a reactive functional group (such as an isocyanate group) The second polymer can be synthesized by reacting the compound having a group represented by the formula The second polymer to be synthesized may contain a branched structure based on a side reaction such as trimerization of an isocyanate group.

The molding composition may contain a polymerization initiator for polymerization of the radically polymerizable monomer. The polymerization initiator may be a thermal radical polymerization initiator, a photo radical polymerization initiator, or a combination thereof. The content of the polymerization initiator is appropriately adjusted in a usual range, and may be, for example, from 0.01 to 5% by mass based on the mass of the molding composition.

Examples of the thermal radical polymerization initiator include organic peroxides such as ketone peroxide, peroxyketal, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxydicarbonate, and hydroperoxide, sodium persulfate, potassium persulfate, Azobisisobutyronitrile (AIBN), 2,2'-azobis-2,4-dimethylvaleronitrile (ADVN), 2,2'-azobis- Azo compounds such as 2-methylbutyronitrile and 4,4'-azobis-4-cyanovaleric acid, alkyl metals such as sodium ethoxide and tert-butyllithium, 1-methoxy- 2-methyl-1-propene), and the like.

A thermal radical polymerization initiator and a catalyst may be combined. Examples of the catalyst include a metal salt and a compound having a reducing property such as a tertiary amine compound such as N, N, N ', N'-tetramethylethylenediamine.

As the photo radical polymerization initiator, 2,2-dimethoxy-1,2-diphenylethane-1-one can be mentioned. As a commercial product thereof, there is Irgacure 651 (manufactured by Nippon Chiba Chemical Co., Ltd.).

The molding composition may contain a solvent, or may be substantially solvent-free. The molding composition may be liquid, semi-solid or solid. The molding composition before curing may be a film type.

The resin molded article can be produced by a method comprising a step of producing a first polymer by radical polymerization of a radically polymerizable monomer in a molding composition. Radical polymerization of a radically polymerizable monomer can be initiated by heating or irradiation of actinic rays such as ultraviolet rays.

The shape and size of the resin molded article (cured product) are not particularly limited. For example, a resin molded article of arbitrary shape can be obtained by curing a molding composition filled in a predetermined mold. The resin molded body may be, for example, a fiber type, a rod type, a column type, a cylinder type, a flat plate type, a disk type, a spiral type, a spherical type or a ring type. The formed body after curing may be further processed by various methods such as machining.

The temperature of the polymerization reaction is not particularly limited, but when the molding composition contains a solvent, the temperature is preferably not higher than its boiling point. The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas, helium gas or argon gas. Thus, inhibition of polymerization by oxygen is suppressed, and a molded article of good quality can be stably obtained.

It is believed that when the radically polymerizable monomer comprising the radically polymerizable compound of formula (I) is polymerized, a cyclic monomer unit of formula (II) is formed. When the radical polymerizable monomer is polymerized in the presence of the first polymer, a structure may be formed in which at least part of the cyclic monomer unit of formula (II) has a cyclic moiety through the second polymer. The following formula (III) schematically shows a structure in which a cyclic moiety of a monomer unit of the formula (II) of the first polymer (A) penetrates through the second polymer (B). In the formula (III), R ⁵ is a monomer unit derived from a radically polymerizable monomer other than the radically polymerizable compound of the formula (I). By the formation of the structure represented by the formula (III), a crosslinked network structure such as a three-dimensional copolymer is formed with the first polymer and the second polymer. In this network structure, it is considered that the degree of freedom of movement of the second polymer passing through the annular portion is maintained to be relatively high. Such a structure is sometimes referred to as a ring structure by those skilled in the art, and the inventors of the present invention contemplate that this contributes to the manifestation of specific properties such as shape memory of the resin molded article. It is not technically easy to directly confirm that the transitional structure is formed. However, for example, since the stress-strain curve obtained by the tensile test of the resin molded article is a so-called J-shaped curve, the formation of the transitional structure is suggested. However, the resin molded article does not necessarily include such a recursive structure.

In the example of the formula (III), the second polymer (B) has a plurality of polyoxyethylene chains and a linking group (L) connecting the terminals thereof. Since the linking group (L) is bulky compared to the polyoxyethylene chain, a state in which the second polymer penetrates the annular portion of the monomer unit of formula (II), such as polyrotaxane, is likely to be maintained. The second polymer can be appropriately selected on the basis of the balance of the size of the cyclic monomer unit, the balance of the inclusion ability and the like, and the characteristics of the polyrotaxane.

The first polymer is produced, and the cured resin molded article may or may not have shape memory property, but a resin molded article having shape memory property can be obtained by appropriately selecting the kind of the radical polymerizable monomer. In the present specification, the term " shape memory property " means that when the resin molded body is deformed by an external force at room temperature (for example, 25 DEG C), the resin molded body retains the deformed shape at room temperature and is heated to a high temperature It means the property of returning to original shape. However, the resin molded article may not completely recover the same shape as the original shape by heating. The heating temperature for shape recovery is, for example, 70 deg.

When the cured resin molded article has shape memory property, usually a first polymer is produced, and the shape of the resin molded article at the time of curing becomes a basic shape. The resin molded body deformed by an external force is deformed to approach this basic shape by heating. A resin molded article having a desired shape as a basic shape can be obtained by curing the resin molded article in a mold having a predetermined shape.

The storage modulus of the resin molded article at 25 캜 is not particularly limited, but may be 0.5 MPa or more. A resin molding having a storage elastic modulus of 0.5 MPa or more generally has shape memory. The modulus of elasticity of the resin molded article may be 1.0 MPa or more, 10 MPa or more, 10 GPa or less, 5 GPa or 500 MPa or less. Since the storage elastic modulus is high, the resin molded article tends to be easily retained in its deformed shape. The resin molded article tends to recover its original shape upon heating because of having an appropriate storage elastic modulus. The modulus of elasticity of the resin molded article can be controlled on the basis of, for example, the type and proportion of the radical polymerizable monomer, the molecular weight of the second polymer, and the amount of the radical polymerization initiator.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Curable resin composition)

1. Synthesis of Polymer Containing Polyoxyalkylene Chain (Modifying Polymer)

Polymer 1

The diol was added to a 20 mL eggplant as shown in Table 1 (mg), then the inside of the flask was replaced with nitrogen, and the contents were melted at 115 ° C. 4,4'-dicyclohexylmethane diisocyanate (262 mg, 1.00 mmol) was added to the melt, and the mixture was stirred at 115 ° C for 24 hours under a nitrogen atmosphere to obtain Polymer 1 containing a polyoxypropylene chain.

The GPC chromatogram of the obtained polymer was obtained using DMF (N, N-dimethylformamide) containing 10 mM lithium bromide as an eluent at a flow rate of 1 mL / min. From the obtained chromatogram, the number-average molecular weight Mn of the polymer was determined as a standard polystyrene conversion value.

The degree of crystallization of the polyoxyethylene chain of the polymer was calculated based on the amount of heat of fusion obtained from the DSC measurement. The heat of fusion of polyethylene glycol alone and the heat of fusion of the synthesized polymer were measured by DSC and the ratio of the polyoxyethylene chain (mass of polyoxyethylene chain / mass of polyoxyalkylene chain) The crystallinity was calculated.

Crystallinity = heat of fusion of polymer x ratio of polyoxyethylene chain (w / w) / heat of fusion of polyethylene glycol ... (One)

Polymers 2 to 11

Polymers 2 to 10 were synthesized in the same manner as Polymer 1, except that the kind and amount of diol and the amount of 4,4'-dicyclohexylmethane diisocyanate were changed in the ratios shown in Table 1. A polyethylene glycol-polypropylene glycol block copolymer having a number average molecular weight of 8300 was prepared and used as the polymer 11.

2. Preparation of curable resin composition

The modifying polymer, the radical polymerizable monomer and the radical polymerization initiator were mixed at the mass ratios shown in Tables 2 and 3 to obtain curable resin compositions of Examples and Comparative Examples.

In Comparative Examples 3 and 4, an acrylic rubber (TAYASA RESIN SG-708-6T (trade name), manufactured by Nagase Chemtech) or silicon (KR-480 (trade name), manufactured by Shin-Etsu Silicones) was used instead of the modified modifying polymer .

3. Production of resin cured product

The curable resin composition was placed in a mold made of glass having a cavity of 40 mm x 50 mm x 0.2 mm or 50 mm x 50 mm x 0.2 mm and the top and bottom were sandwiched by a glass plate and exposed by a UV exposure device (UV-XeFL, At room temperature to obtain a plate-like resin cured product. And the accumulated light quantity was changed from 365 nm to 200 mJ / cm2.

4. Tensile test

A specimen having a size of 5 mm x 50 mm was punched out from the cured resin. Three portions of the test piece corresponding to the spaces between the chucks were marked at the three positions in the longitudinal direction, and the distances between the marks were set as L0 and L0 '. Tensile test was carried out using a tensile tester (EZ-TEST manufactured by Shimadzu Corporation) at a measurement temperature of 25 占 폚, a tensile speed of 10 mm / min, and a chuck distance L1 of 30 mm. In the test piece immediately after the fracture, a two-point mark with no broken portion between the markers among the three markers was selected and the distance (L2) between the markers was measured. When the initial length corresponding to this portion is L0, the elongation at break is calculated by the formula: (L2-L0) / L0. Alternatively, the fracture elongation may be calculated by the formula: (L3-L1) / L1 using the chuck distance L3 at the time of fracture.

(L2-L4) / (L2-L0) wherein the ratio of the elongation to the elongation at break was measured by measuring the distance (L4) between the markers after heating at 70 deg. ). The distance L2 immediately after the fracture may be calculated by the formula: L2 = L3 x (L0 / L1) using the chuck distance L3. A large elastic elongation percentage means that the shape recovery property after being deformed by stress is excellent.

5. Endurance curve

A film-shaped resin cured product (50 mm x 50 mm x 0.2 mm) was folded twice, and a pressure of 1 N / cm < 2 > was applied to the fold line in this state for 5 minutes. The folded line portion was returned to its original state, and the portion was observed with an eye under an optical microscope (10 times). The change in appearance and the abnormality such as whitening and voids were observed compared to before bending. The evaluation criteria are as follows.

A: No abnormality was observed in optical microscope observation

B: No abnormality is observed by eyes, but abnormality is confirmed by optical microscope

C: The eye is seen as abnormal or the fold line is broken.

The curable resin compositions of Examples 1 to 12 containing the polymer 1 to 9 or 11 containing a polyoxyalkylene chain had higher breaking elongation as compared with the curable resin composition of Comparative Example 1 which did not contain the modifying polymer It is possible to form a resin molded article excellent in shape recovery after being deformed under stress. Polymer 10 containing no polyoxyalkylene chain could not be dissolved in a radically polymerizable monomer, and in Comparative Example 2, a uniform curable resin composition could not be prepared. Further, the acrylic rubber or the mixture of silicone and the radically polymerizable monomer caused phase separation, and in Comparative Examples 3 and 4, a uniform curable resin composition could not be prepared.

(Composition for molding)

1. Synthesis

Synthesis Example 1 Synthesis of trans-1,2-bis (2-acryloyloxyethylcarbamoyloxy) cyclohexane (BACH)

Trans-1,2-cyclohexanediol (2.32 g, 20.0 mmol) was added to a 100 mL two-necked flask, and the flask was purged with nitrogen. Dichloromethane (40 mL) and dibutyltin dilaurate (11.8 L, 0.10 mol%: 0.020 mmol) were added thereto. Dichloromethane (4 mL) of 2-acryloyloxyethyl isocyanate (5.93 g, 42.0 mmol) was added dropwise from the dropping funnel to the reaction solution in the flask, and the reaction solution was stirred at 30 ° C for 24 hours to carry out the reaction . After completion of the reaction, diethyl ether was added to the reaction mixture, and the mixture was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. A solution containing the desired product was isolated from the residue by silica gel chromatography (developing solvent: chloroform) and concentrated. The resulting crude product was purified by recrystallization from diethyl ether and hexane to obtain BACH white crystals. The yield was 3.78 g and the yield was 47.4 mass%.

Synthesis Example 2: Synthesis of PEG-PPG oligomer 1

Polyethylene glycol (PEG1500, 750 mg, 0.500 mmol, number average molecular weight 1500) and polypropylene glycol (PPG4000, 2000 mg, 0.500 mmol, number average molecular weight 4000) were added to a 20 mL eggplant type flask and then the inside of the flask was replaced with nitrogen, Lt; RTI ID = 0.0 > 115 C. < / RTI & 4,4'-dicyclohexylmethane diisocyanate (262 mg, 1.00 mmol) was added to the melt, and the melt was stirred at 115 ° C under a nitrogen atmosphere for 24 hours to obtain PEG-PPG oligomer 1 (polyoxyethylene chain and poly A second polymer containing an oxypropylene chain).

The oligomer 1 thus obtained had a weight average molecular weight (Mw) of 9,300 and an oligomer 1 had a weight average molecular weight / number average molecular weight (Mw / Mn) of 1.65.

Synthesis Example 3: Synthesis of PEG-PPG oligomer 2

Polyethylene glycol (PEG1500, 750 mg, 0.500 mmol, number average molecular weight 1500) and polypropylene glycol (PPG4000, 2000 mg, 0.500 mmol, number average molecular weight 4000) were added to a 20 mL eggplant type flask and then the inside of the flask was replaced with nitrogen, Lt; RTI ID = 0.0 > 115 C. < / RTI & Dicyclohexylmethane diisocyanate (262 mg, 1.00 mmol) and dibutyltin laurylate (11.8 쨉 L, 0.10 mol%: 0.020 mmol) were added to the melting solution and the mixture was stirred at 115 째 C in a molten liquid Was stirred for 24 hours to obtain a PEG-PPG oligomer 2 (a second polymer having a polyoxyethylene chain and a polyoxypropylene chain).

The oligomer 2 thus obtained had a weight average molecular weight (Mw) of 50,000, and a weight average molecular weight / number average molecular weight (Mw / Mn) of oligomer 2 of 1.95.

2. Measurement of molecular weight

GPC chromatogram of the oligomer was obtained at a flow rate of 1 mL / min using DMF (N, N-dimethylformamide) containing 10 mM of lithium bromide as an eluent. From the obtained chromatogram, the number average molecular weight and the weight average molecular weight of the oligomer were determined as polystyrene conversion values.

3. Molding composition and resin molded article

(Example 2-1)

(27.7 mg, 69.5 μmol) of Synthesis Example 1, PEG-PPG oligomer 1 of Synthesis Example 2 (34.5 mg, 2.88 μmol), 2-ethylhexyl acrylate (2-EHA, 553 mg, 3.00 mmol) Nitrile (AN, 390 mg, 3.00 mmol) and Irgacure 651 (15.5 mg, 60.5 μmol) were heated and dissolved in a sample bottle to prepare a compounding liquid (molding composition).

The obtained compounding liquid was introduced into a stainless steel mold having a length × width × depth of 46 mm × 10 mm × 1 mm, and a transparent sheet made of polyethylene terephthalate was placed thereon. On the transparent sheet, UV (ultraviolet ray) was irradiated for 30 minutes at room temperature (25 캜, the same applies to the following) to photo-cure the blend liquid to obtain a film-shaped molded article.

A polytetrafluoroethylene tube (trade name: Naflon (registered trademark) BT tube 1 / 8B) having an inner diameter of 1.59 mmφ, an outer diameter of 3.17 mmφ and a thickness of 0.79 mm was wound around a stainless steel tube having an outer diameter of 10 mmφ. The blended liquid was charged into the wound tube and irradiated with ultraviolet rays at room temperature for 30 minutes to photo-cure the blended liquid in the tube. Thereafter, the spiral-shaped molded body was taken out of the tube.

The blended liquid filled in a cup-shaped mold made of polyethylene was photo-cured by ultraviolet irradiation at room temperature for 30 minutes. The cup-shaped molded body was taken out from the mold as a three-dimensional molded body.

(Comparative Example 2-1)

A blend was prepared in the same manner as in Example 1 except that PEG-PPG oligomer 1 was not used. Using the obtained compounding liquid, resin molding bodies of various shapes were produced in the same manner as in Example 2-1.

(Examples 2-2, 2-3 and Reference Example)

The compounding solution was prepared at the compounding ratio shown in Table 4. Using the obtained compounding liquid, resin molding bodies of various shapes were produced in the same manner as in Example 2-1.

4. Evaluation of storage elasticity

A test piece of short-stitch type having a width of 5 mm and a length of 30 mm was cut out from the film-shaped molded article. Using this test piece, the storage modulus at 25 占 폚 was measured using a dynamic viscoelasticity measuring apparatus (RSA-G2) manufactured by TA Instruments. The measurement conditions are as follows.

· Chuck distance: 20 mm

· Measuring frequency: 10 Hz

· Temperature rise rate 5 ℃ / min

Shape memory

The film-shaped molded article was folded twice and folded lines were pressed into a glass tube in this state. And confirmed that the folded shape did not substantially return to its original shape. The spiral shaped body was stretched and deformed into a rod shape. The cup-shaped formed article was sandwiched between two glass plates and deformed by crushing by pressing in the height direction. It was judged as "good" when the molded body of each shape retained the shape after deformation, and "poor" when not.

Thereafter, the deformed formed article was immersed in water at 70 캜 and visually observed to return to the initial shape within 10 seconds immediately after immersion. The case where the molded body recovered its initial shape was judged as " good ", and the case where it was not recovered was judged as " defective ".

Bending

The folded line portion of the film-shaped formed body of the example was returned to its original state, and the portion was observed with an eye under an optical microscope (100 times). The case where there was no change in appearance compared with that before the bending was evaluated as " good ", and the case where an abnormality such as whitening and voids occurred was judged as " defective ".

Measurement of breaking strength and elongation at break

A film made of polyethylene terephthalate (PET) was laid on a stainless steel mold having a length × width × depth of 46 mm × 10 mm × 1 mm. A resin composition was introduced into the solution, and a PET transparent sheet was placed thereon. On the transparent sheet, ultraviolet light of 2000 mJ / cm 2 was irradiated at room temperature (25 ° C, the same applies hereinafter) to obtain a resin film.

A test piece (width: 8 mm, thickness: 1 mm) was cut out from the obtained resin film. The test piece was measured for breaking strength and elongation at break at room temperature, a chuck distance of 30 mm, and a tensile rate of 10.0 mm / min using Strogram T (manufactured by YOSEI SEISAKUSHO Co., Ltd.) did.

The resin molded articles of the respective Examples had excellent bending strength and showed a high elongation. In addition, the resin molded articles of the respective Examples had good shape memory properties. From these results, it was confirmed that according to one aspect of the present invention, a resin molded article having shape memory property excellent in shape recovery property by heating can be obtained.

1:

Claims (21)

A radically polymerizable monomer comprising a monofunctional radically polymerizable monomer,
A linear or branched polymer containing a polyoxyalkylene chain,
Radical polymerization initiator
Based on the weight of the curable resin composition. The curable resin composition according to claim 1, wherein the polyoxyalkylene chain is a polyoxyethylene chain, a polyoxypropylene chain, or a combination thereof. The curable resin composition according to claim 1 or 2, wherein the polymer is a reaction product of a bifunctional alcohol having a polyoxyalkylene chain and a bifunctional isocyanate. The curable resin composition according to claim 3, wherein the bifunctional alcohol has a number average molecular weight of 500 to 20,000. The curable resin composition according to any one of claims 1 to 4, wherein the proportion of the polyoxyalkylene chain in the polymer is 20 to 60 mass% based on the mass of the polymer. The curable resin composition according to any one of claims 1 to 5, wherein the polymer has a number average molecular weight of 3000 to 150000. The curable resin composition according to any one of claims 1 to 6, wherein the polymer comprises at least two polyoxyalkylene chains and a linking group linking them, and the linking group has a cyclic group. The curable resin composition according to any one of claims 1 to 7, wherein the content of the polymer is 1 to 20 mass% based on the mass of the curable resin composition. 9. The curable resin composition according to any one of claims 1 to 8, wherein the monofunctional radically polymerizable monomer comprises an alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms which may have a substituent. 10. The curable resin composition according to any one of claims 1 to 9, wherein the monofunctional radically polymerizable monomer comprises acrylonitrile. 11. The curable resin composition according to any one of claims 1 to 10, wherein the radical polymerization initiator is a photo radical polymerization initiator. Formula (I):

, Wherein X, R ¹ and R ² are each independently a divalent organic group, and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, and a monofunctional radically polymerizable monomer, As a second polymer,
A second polymer which is linear or branched,
And a storage elastic modulus at 25 占 폚 of 0.5 MPa or more. Formula (I):

, Wherein X, R ¹ and R ² are each independently a divalent organic group, and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, and a monofunctional radically polymerizable monomer, As a second polymer,
A second polymer which is linear or branched,
A resin molded article having shape memory property. The resin molded article according to claim 12 or 13, wherein the second polymer is a polymer containing a polyoxyalkylene chain. 15. The resin molded article according to any one of claims 12 to 14, wherein the monofunctional radically polymerizable monomer comprises an alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms which may have a substituent. 16. The resin molded article according to any one of claims 12 to 15, wherein the monofunctional radically polymerizable monomer comprises acrylonitrile. 17. The compound according to any one of claims 12 to 16, wherein X in the formula (I)

, Y is a cyclic group which may have a substituent, Z ¹ and Z ² are each independently a functional group containing an atom selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom, and i and j are respectively Independently represents an integer of 0 to 2, and * represents a group representing a bond. The resin molded article according to any one of claims 12 to 17, wherein the second polymer has a weight average molecular weight of 5,000 or more. Formula (I):

, Wherein X, R ¹ and R ² are each independently a divalent organic group and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, and a radical containing a monofunctional radically polymerizable monomer A polymerizable monomer,
The second polymer in linear or branched form
, Wherein the molding composition
Wherein the molding composition forms a resin molding having a storage elastic modulus at 25 占 폚 of at least 0.5 MPa when the radically polymerizable monomer is polymerized to form the first polymer in the presence of the second polymer. Formula (I):

, Wherein X, R ¹ and R ² are each independently a divalent organic group and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, and a radical containing a monofunctional radically polymerizable monomer A polymerizable monomer,
The second polymer in linear or branched form
, Wherein the molding composition
Wherein the molding composition forms a resin molding having shape memory when the radical polymerizable monomer is polymerized to form the first polymer in the presence of the second polymer. A method for producing a resin molded article comprising a first polymer and a linear or branched second polymer,
Formula (I):

, Wherein X, R ¹ and R ² are each independently a divalent organic group and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, and a radical containing a monofunctional radically polymerizable monomer And a step of producing the first polymer by polymerization of the radically polymerizable monomer in a molding composition comprising the polymerizable monomer and the second polymer.

Images